# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_p21 _audit_creation_date 2013-07-22T15:19:15-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C8 H12 Cu2 O14, 4(H2 O)' _chemical_formula_sum 'C8 H20 Cu2 O18' _chemical_formula_weight 531.32 _chemical_compound_source 'synthesis as described' _chemical_absolute_configuration ad #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21' _symmetry_space_group_name_Hall 'P 2yb' _symmetry_Int_Tables_number 4 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 8.3500(11) _cell_length_b 8.7471(12) _cell_length_c 12.0392(17) _cell_angle_alpha 90 _cell_angle_beta 104.276(7) _cell_angle_gamma 90 _cell_volume 852.2(2) _cell_formula_units_Z 2 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 4620 _cell_measurement_theta_min 2.5124 _cell_measurement_theta_max 25.0132 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description block _exptl_crystal_colour blue _exptl_crystal_size_max 0.6 _exptl_crystal_size_mid 0.48 _exptl_crystal_size_min 0.39 _exptl_crystal_density_diffrn 2.071 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 540 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 2.593 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details '(SADABS; Sheldrick, 2003)' _exptl_absorpt_correction_T_min 0.2048 _exptl_absorpt_correction_T_max 0.3638 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_source 'sealed x-ray tube' _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_detector 'APEX-II CCD' _diffrn_orient_matrix_type 'x-axis to radiation source' _diffrn_orient_matrix_ub_11 -0.783315E-1 _diffrn_orient_matrix_ub_12 -0.574057E-1 _diffrn_orient_matrix_ub_13 -0.620498E-1 _diffrn_orient_matrix_ub_21 0.949361E-1 _diffrn_orient_matrix_ub_22 -0.544663E-1 _diffrn_orient_matrix_ub_23 -0.189907E-1 _diffrn_orient_matrix_ub_31 -0.818407E-2 _diffrn_orient_matrix_ub_32 -0.82372E-1 _diffrn_orient_matrix_ub_33 0.0558 _diffrn_measurement_device_type 'Bruker APEX-II' _diffrn_measurement_method '\f or \w oscillation scans' _diffrn_reflns_av_R_equivalents 0.0318 _diffrn_reflns_av_unetI/netI 0.048 _diffrn_reflns_number 5626 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.52 _diffrn_reflns_theta_max 25.05 _diffrn_reflns_theta_full 25.05 _diffrn_measured_fraction_theta_full 0.995 _diffrn_measured_fraction_theta_max 0.995 _reflns_number_total 2608 _reflns_number_gt 2532 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Bruker APEX2 software' _computing_cell_refinement 'SAINT V7.66A integration software' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0236P)^2^+0.0845P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method SHELXL _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_extinction_coef 0.063(2) _refine_ls_number_reflns 2608 _refine_ls_number_parameters 254 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.024 _refine_ls_R_factor_gt 0.0233 _refine_ls_wR_factor_ref 0.0607 _refine_ls_wR_factor_gt 0.0603 _refine_ls_goodness_of_fit_ref 1.027 _refine_ls_restrained_S_all 1.027 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.003(13) _refine_diff_density_max 0.352 _refine_diff_density_min -0.462 _refine_diff_density_rms 0.069 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cu1 Cu 0.19191(4) 0.11136(4) 0.52642(3) 0.01021(12) Uani 1 1 d . . . Cu2 Cu 0.33140(4) 0.11234(4) 0.97717(3) 0.00914(12) Uani 1 1 d . . . O1 O 0.3353(2) -0.0643(2) 0.53085(18) 0.0134(5) Uani 1 1 d . . . O2 O 0.3719(2) -0.3066(3) 0.58636(19) 0.0164(5) Uani 1 1 d . . . O3 O 0.1850(2) -0.0621(2) 0.95147(18) 0.0115(5) Uani 1 1 d . . . O4 O 0.0976(3) -0.2804(3) 0.86392(19) 0.0183(5) Uani 1 1 d . . . O5 O 0.1146(2) -0.0090(2) 0.64526(16) 0.0094(5) Uani 1 1 d . . . H5A H 0.0105 -0.0078 0.6366 0.014 Uiso 1 1 d R . . O7 O 0.0549(2) 0.2824(3) 0.54201(18) 0.0125(5) Uani 1 1 d . . . O8 O 0.0041(3) 0.4993(3) 0.62297(18) 0.0167(6) Uani 1 1 d . . . O9 O 0.4637(2) 0.2959(3) 0.98402(19) 0.0148(5) Uani 1 1 d . . . O10 O 0.4822(2) 0.5256(3) 0.90686(18) 0.0125(5) Uani 1 1 d . . . O11 O 0.3551(2) 0.2521(2) 0.68850(17) 0.0114(5) Uani 1 1 d . . . H11A H 0.4481 0.2845 0.6866 0.017 Uiso 1 1 d R . . O12 O 0.1765(2) 0.2359(2) 0.85467(17) 0.0101(5) Uani 1 1 d . . . H12A H 0.071 0.2456 0.854 0.015 Uiso 1 1 d R . . O81 O 0.3018(2) 0.2146(3) 0.41986(18) 0.0173(5) Uani 1 1 d . . . H81A H 0.3994 0.1894 0.4342 0.026 Uiso 1 1 d R . . H81B H 0.286 0.31 0.4152 0.026 Uiso 1 1 d R . . O82 O 0.2208(2) 0.1809(3) 1.1335(2) 0.0222(6) Uani 1 1 d . . . H82A H 0.1199 0.1857 1.1118 0.033 Uiso 1 1 d R . . H82B H 0.2601 0.1294 1.1912 0.033 Uiso 1 1 d R . . O91 O -0.2158(2) 0.0116(3) 0.6106(2) 0.0196(6) Uani 1 1 d . . . H91A H -0.2437 0.0145 0.6826 0.029 Uiso 1 1 d R . . H91B H -0.2565 0.0934 0.5631 0.029 Uiso 1 1 d R . . O92 O -0.3595(3) 0.3825(4) 0.6910(2) 0.0478(9) Uani 1 1 d . . . H92A H -0.3025 0.4279 0.6514 0.072 Uiso 1 1 d R . . H92B H -0.2953 0.3599 0.7553 0.072 Uiso 1 1 d R . . O93 O -0.2768(2) -0.0057(3) 0.8260(2) 0.0256(6) Uani 1 1 d . . . H93A H -0.2462 -0.0896 0.8387 0.038 Uiso 1 1 d R . . H93B H -0.3838 0.0014 0.8094 0.038 Uiso 1 1 d R . . O94 O -0.1222(2) 0.2702(3) 0.87077(18) 0.0185(5) Uani 1 1 d . . . H94A H -0.1389 0.1758 0.8864 0.028 Uiso 1 1 d R . . H94B H -0.1219 0.3183 0.9329 0.028 Uiso 1 1 d R . . C1 C 0.3087(4) -0.1781(4) 0.5893(3) 0.0102(7) Uani 1 1 d . . . C2 C 0.1953(4) -0.1548(4) 0.6703(3) 0.0091(7) Uani 1 1 d . . . H2A H 0.1134 -0.2371 0.6605 0.011 Uiso 1 1 calc R . . C3 C 0.2981(4) -0.1486(4) 0.7948(3) 0.0094(7) Uani 1 1 d . . . H3A H 0.3738 -0.2361 0.8077 0.011 Uiso 1 1 calc R . . C4 C 0.1836(4) -0.1635(4) 0.8760(3) 0.0106(7) Uani 1 1 d . . . C5 C 0.0920(4) 0.3881(4) 0.6182(3) 0.0099(7) Uani 1 1 d . . . C6 C 0.2585(4) 0.3813(4) 0.7067(3) 0.0093(7) Uani 1 1 d . . . H6A H 0.3202 0.4737 0.6972 0.011 Uiso 1 1 calc R . . C7 C 0.2407(4) 0.3799(4) 0.8296(3) 0.0084(7) Uani 1 1 d . . . H7A H 0.1658 0.4621 0.8398 0.01 Uiso 1 1 calc R . . C8 C 0.4089(4) 0.4023(4) 0.9130(3) 0.0104(7) Uani 1 1 d . . . O6 O 0.3949(2) -0.0117(2) 0.81522(17) 0.0097(5) Uani 1 1 d . . . H6B H 0.3513 0.0613 0.7661 0.015 Uiso 1 1 d R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cu1 0.01158(19) 0.0087(2) 0.0114(2) 0.00186(18) 0.00478(14) 0.0015(2) Cu2 0.00896(19) 0.0075(2) 0.0102(2) 0.00057(18) 0.00087(13) -0.0007(2) O1 0.0144(11) 0.0116(12) 0.0168(12) 0.0034(10) 0.0089(9) 0.0011(9) O2 0.0205(12) 0.0099(13) 0.0215(13) 0.0011(10) 0.0102(10) 0.0048(10) O3 0.0124(11) 0.0117(12) 0.0125(12) -0.0040(10) 0.0070(9) -0.0009(9) O4 0.0207(12) 0.0162(13) 0.0217(14) -0.0049(11) 0.0123(10) -0.0098(10) O5 0.0069(10) 0.0108(11) 0.0106(11) 0.0004(9) 0.0021(8) 0.0020(8) O7 0.0098(11) 0.0126(12) 0.0139(12) -0.0005(10) 0.0006(9) 0.0000(9) O8 0.0179(12) 0.0150(13) 0.0138(12) -0.0036(10) -0.0026(9) 0.0102(10) O9 0.0128(11) 0.0144(12) 0.0133(12) 0.0035(10) -0.0041(9) 0.0001(9) O10 0.0136(11) 0.0093(11) 0.0121(12) 0.0004(9) -0.0015(9) -0.0058(9) O11 0.0075(10) 0.0126(12) 0.0147(12) 0.0009(10) 0.0038(9) 0.0030(9) O12 0.0070(10) 0.0097(12) 0.0137(12) 0.0025(9) 0.0030(9) -0.0006(8) O81 0.0188(11) 0.0125(11) 0.0222(14) 0.0064(11) 0.0083(10) 0.0030(10) O82 0.0197(12) 0.0275(15) 0.0211(14) -0.0024(11) 0.0083(10) -0.0006(10) O91 0.0206(12) 0.0113(12) 0.0295(14) 0.0009(10) 0.0109(10) 0.0049(10) O92 0.0274(15) 0.089(2) 0.0318(16) 0.0314(16) 0.0158(13) 0.0041(15) O93 0.0130(12) 0.0207(13) 0.0452(17) 0.0030(13) 0.0112(11) 0.0016(10) O94 0.0197(12) 0.0206(13) 0.0176(13) -0.0039(10) 0.0089(10) 0.0001(10) C1 0.0082(15) 0.0115(17) 0.0091(16) -0.0012(14) -0.0014(12) 0.0016(13) C2 0.0080(16) 0.0089(16) 0.0111(17) 0.0025(14) 0.0038(13) -0.0010(13) C3 0.0095(15) 0.0093(16) 0.0113(18) -0.0047(15) 0.0061(13) -0.0014(13) C4 0.0063(15) 0.0135(17) 0.0124(17) 0.0042(14) 0.0033(13) -0.0008(13) C5 0.0105(16) 0.0114(17) 0.0080(16) 0.0033(14) 0.0028(13) 0.0005(13) C6 0.0082(16) 0.0069(17) 0.0119(19) 0.0024(15) 0.0005(13) 0.0011(12) C7 0.0032(16) 0.0065(15) 0.0136(17) -0.0003(13) -0.0015(13) -0.0005(12) C8 0.0121(16) 0.0105(17) 0.0097(16) -0.0037(13) 0.0046(13) 0.0000(13) O6 0.0095(10) 0.0095(11) 0.0101(11) 0.0032(9) 0.0021(9) -0.0011(8) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu1 O7 1.921(2) . ? Cu1 O1 1.941(2) . ? Cu1 O81 1.971(2) . ? Cu1 O5 2.007(2) . ? Cu1 O8 2.329(2) 2_546 ? Cu1 O11 2.423(2) . ? Cu2 O3 1.932(2) . ? Cu2 O9 1.939(2) . ? Cu2 O10 1.969(2) 2_647 ? Cu2 O12 2.019(2) . ? Cu2 O82 2.369(2) . ? Cu2 O6 2.402(2) . ? O1 C1 1.269(4) . ? O2 C1 1.246(4) . ? O3 C4 1.268(4) . ? O4 C4 1.237(4) . ? O5 C2 1.439(4) . ? O5 H5A 0.8492 . ? O7 C5 1.285(4) . ? O8 C5 1.228(4) . ? O8 Cu1 2.329(2) 2_556 ? O9 C8 1.271(4) . ? O10 C8 1.251(4) . ? O10 Cu2 1.969(2) 2_657 ? O11 C6 1.436(4) . ? O11 H11A 0.8319 . ? O12 C7 1.431(4) . ? O12 H12A 0.8832 . ? O81 H81A 0.8199 . ? O81 H81B 0.8454 . ? O82 H82A 0.8199 . ? O82 H82B 0.8248 . ? O91 H91A 0.9514 . ? O91 H91B 0.9267 . ? O92 H92A 0.8501 . ? O92 H92B 0.8494 . ? O93 H93A 0.7804 . ? O93 H93B 0.8681 . ? O94 H94A 0.8652 . ? O94 H94B 0.8585 . ? C1 C2 1.531(4) . ? C2 C3 1.533(4) . ? C2 H2A 0.98 . ? C3 O6 1.432(4) . ? C3 C4 1.533(4) . ? C3 H3A 0.98 . ? C5 C6 1.530(4) . ? C6 C7 1.523(5) . ? C6 H6A 0.98 . ? C7 C8 1.524(4) . ? C7 H7A 0.98 . ? O6 H6B 0.8854 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O7 Cu1 O1 172.98(9) . . ? O7 Cu1 O81 95.22(10) . . ? O1 Cu1 O81 89.85(9) . . ? O7 Cu1 O5 92.01(9) . . ? O1 Cu1 O5 82.51(9) . . ? O81 Cu1 O5 171.00(8) . . ? O7 Cu1 O8 94.66(8) . 2_546 ? O1 Cu1 O8 89.96(9) . 2_546 ? O81 Cu1 O8 92.38(8) . 2_546 ? O5 Cu1 O8 92.36(8) . 2_546 ? O7 Cu1 O11 75.86(8) . . ? O1 Cu1 O11 99.19(8) . . ? O81 Cu1 O11 91.82(9) . . ? O5 Cu1 O11 84.75(7) . . ? O8 Cu1 O11 169.94(7) 2_546 . ? O3 Cu2 O9 172.84(9) . . ? O3 Cu2 O10 99.64(9) . 2_647 ? O9 Cu2 O10 86.93(9) . 2_647 ? O3 Cu2 O12 92.28(8) . . ? O9 Cu2 O12 81.00(9) . . ? O10 Cu2 O12 167.56(9) 2_647 . ? O3 Cu2 O82 88.39(8) . . ? O9 Cu2 O82 94.95(9) . . ? O10 Cu2 O82 85.93(8) 2_647 . ? O12 Cu2 O82 98.05(8) . . ? O3 Cu2 O6 76.75(8) . . ? O9 Cu2 O6 99.84(8) . . ? O10 Cu2 O6 96.16(8) 2_647 . ? O12 Cu2 O6 83.03(8) . . ? O82 Cu2 O6 165.14(8) . . ? C1 O1 Cu1 116.42(19) . . ? C4 O3 Cu2 124.2(2) . . ? C2 O5 Cu1 113.44(17) . . ? C2 O5 H5A 116.7 . . ? Cu1 O5 H5A 113.9 . . ? C5 O7 Cu1 125.82(19) . . ? C5 O8 Cu1 127.7(2) . 2_556 ? C8 O9 Cu2 118.1(2) . . ? C8 O10 Cu2 127.1(2) . 2_657 ? C6 O11 Cu1 107.29(15) . . ? C6 O11 H11A 107.4 . . ? Cu1 O11 H11A 119.6 . . ? C7 O12 Cu2 114.83(16) . . ? C7 O12 H12A 109.8 . . ? Cu2 O12 H12A 121.1 . . ? Cu1 O81 H81A 109.7 . . ? Cu1 O81 H81B 113.9 . . ? H81A O81 H81B 114.2 . . ? Cu2 O82 H82A 109.4 . . ? Cu2 O82 H82B 112.3 . . ? H82A O82 H82B 117.4 . . ? H91A O91 H91B 114 . . ? H92A O92 H92B 107.8 . . ? H93A O93 H93B 112.4 . . ? H94A O94 H94B 104.1 . . ? O2 C1 O1 123.9(3) . . ? O2 C1 C2 118.1(3) . . ? O1 C1 C2 118.0(3) . . ? O5 C2 C1 108.4(2) . . ? O5 C2 C3 107.1(2) . . ? C1 C2 C3 110.0(3) . . ? O5 C2 H2A 110.4 . . ? C1 C2 H2A 110.4 . . ? C3 C2 H2A 110.4 . . ? O6 C3 C2 110.7(2) . . ? O6 C3 C4 112.1(2) . . ? C2 C3 C4 109.5(3) . . ? O6 C3 H3A 108.2 . . ? C2 C3 H3A 108.2 . . ? C4 C3 H3A 108.2 . . ? O4 C4 O3 124.5(3) . . ? O4 C4 C3 115.5(3) . . ? O3 C4 C3 120.0(3) . . ? O8 C5 O7 124.1(3) . . ? O8 C5 C6 116.7(3) . . ? O7 C5 C6 119.1(3) . . ? O11 C6 C7 109.6(2) . . ? O11 C6 C5 111.9(3) . . ? C7 C6 C5 112.8(3) . . ? O11 C6 H6A 107.5 . . ? C7 C6 H6A 107.5 . . ? C5 C6 H6A 107.5 . . ? O12 C7 C6 110.1(2) . . ? O12 C7 C8 107.8(2) . . ? C6 C7 C8 110.1(3) . . ? O12 C7 H7A 109.6 . . ? C6 C7 H7A 109.6 . . ? C8 C7 H7A 109.6 . . ? O10 C8 O9 124.8(3) . . ? O10 C8 C7 117.2(3) . . ? O9 C8 C7 118.0(3) . . ? C3 O6 Cu2 106.82(15) . . ? C3 O6 H6B 111.5 . . ? Cu2 O6 H6B 94.6 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O5 H5A O91 0.85 1.85 2.692(3) 174.8 . O11 H11A O92 0.83 1.81 2.635(3) 171 1_655 O12 H12A O94 0.88 1.69 2.566(3) 172.6 . O81 H81A O2 0.82 1.99 2.750(3) 154.8 2_656 O81 H81B O91 0.85 1.86 2.696(3) 170.2 2_556 O82 H82A O4 0.82 1.93 2.688(3) 153 2_557 O82 H82B O92 0.82 2.6 3.378(4) 156.6 2_547 O91 H91A O93 0.95 1.82 2.767(3) 171.2 . O91 H91B O2 0.93 2.02 2.886(3) 155 2_556 O92 H92A O1 0.85 2.14 2.767(3) 129.8 2_556 O92 H92A O81 0.85 2.65 3.281(4) 132 2_556 O92 H92B O94 0.85 1.91 2.732(3) 162.5 . O93 H93A O82 0.78 2.04 2.804(3) 167.2 2_547 O93 H93B O6 0.87 1.87 2.713(3) 163.2 1_455 O94 H94A O93 0.87 1.99 2.727(3) 142.2 . O94 H94B O3 0.86 1.92 2.750(3) 163.6 2_557 O94 H94B O4 0.86 2.55 3.181(3) 130.6 2_557 O6 H6B O11 0.89 1.92 2.741(3) 154.2 . O6 H6B O5 0.89 2.23 2.703(3) 112.8 . # The following lines are used to test the character set of files sent by # network email or other means. They are not part of the CIF data set # abcdefghijklmnopqrstuvwxyzABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789 # !@#$%^&*()_+{}:"~<>?|\-=[];'`,./ # END of CIF _database_code_depnum_ccdc_archive 'CCDC 927768' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_p21212 _audit_creation_date 2013-07-24T09:04:45-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C4 H4 Cu1 O6' _chemical_formula_sum 'C4 H4 Cu O6' _chemical_formula_weight 211.61 _chemical_compound_source 'synthesis as described' _chemical_absolute_configuration ad #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _space_group_crystal_system orthorhombic _space_group_name_H-M_alt 'P 21 21 2' _space_group_name_Hall 'P 2 2ab' _space_group_IT_number 18 loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, -y, z' 'x+1/2, -y+1/2, -z' '-x+1/2, y+1/2, -z' _cell_length_a 11.7511(13) _cell_length_b 4.9808(5) _cell_length_c 8.9689(11) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 524.95(10) _cell_formula_units_Z 4 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used 1065 _cell_measurement_theta_min 2.86 _cell_measurement_theta_max 24.9864 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description needle _exptl_crystal_colour blue _exptl_crystal_size_max 0.21 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.02 _exptl_crystal_density_diffrn 2.678 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 420 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 4.133 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; (SADABS- Sheldrick, 2003) Comment on transmission values: The program SADABS (v2.06) outputs the ratio of minimum to maximum apparent transmission (0.740577). We have set T(max) to the expected value, i.e. exp(-r_min*mu) and we calculate T(min) from the minimum to maximum apparent transmission given by SADABS. ; _exptl_absorpt_correction_T_min 0.6818 _exptl_absorpt_correction_T_max 0.9207 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_source 'sealed x-ray tube' _diffrn_ambient_temperature 200(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_detector 'APEX-II CCD' _diffrn_orient_matrix_type 'x-axis to radiation source' _diffrn_orient_matrix_ub_11 -0.738763E-1 _diffrn_orient_matrix_ub_12 -0.146165 _diffrn_orient_matrix_ub_13 0.150967E-1 _diffrn_orient_matrix_ub_21 -0.301869E-1 _diffrn_orient_matrix_ub_22 0.907215E-1 _diffrn_orient_matrix_ub_23 0.723844E-1 _diffrn_orient_matrix_ub_31 -0.778621E-1 _diffrn_orient_matrix_ub_32 0.10351 _diffrn_orient_matrix_ub_33 -0.421235E-1 _diffrn_measurement_device_type 'Bruker APEX-II' _diffrn_measurement_method '\f or \w oscillation scans' _diffrn_reflns_av_R_equivalents 0.055 _diffrn_reflns_av_unetI/netI 0.0633 _diffrn_reflns_number 3046 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -5 _diffrn_reflns_limit_k_max 5 _diffrn_reflns_limit_l_min -7 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.27 _diffrn_reflns_theta_max 25.06 _diffrn_reflns_theta_full 25.06 _diffrn_measured_fraction_theta_full 0.991 _diffrn_measured_fraction_theta_max 0.991 _reflns_number_total 922 _reflns_number_gt 782 _reflns_threshold_expression >2\s(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'Bruker APEX2 software' _computing_cell_refinement 'SAINT V8.18C integration software' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SIR92 (Giacovazzo et al, 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # STRUCTURE SOLUTION #----------------------------------------------------------------------------# _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _refine_special_details ; Due to the poor diffraction quality of the sample crystal, In an attempt to perform anisotropic refinement of the C1 and C3 atoms is not successful. Only isotropic refinement could be applied to the C1 and C3 atoms. Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2\s(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0333P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_number_reflns 922 _refine_ls_number_parameters 90 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0495 _refine_ls_R_factor_gt 0.0368 _refine_ls_wR_factor_ref 0.0788 _refine_ls_wR_factor_gt 0.0751 _refine_ls_goodness_of_fit_ref 1.027 _refine_ls_restrained_S_all 1.027 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.04(4) _refine_diff_density_max 0.641 _refine_diff_density_min -0.564 _refine_diff_density_rms 0.121 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cu1 Cu 0.28876(5) 0.59117(12) 0.25437(10) 0.0113(2) Uani 1 1 d . . . O1 O 0.2841(3) 0.3579(8) 0.4267(4) 0.0119(9) Uani 1 1 d . . . O2 O 0.3280(3) 0.3216(8) 0.6691(5) 0.0128(10) Uani 1 1 d . . . O3 O 0.3180(3) 0.8389(8) 0.0923(5) 0.0115(10) Uani 1 1 d . . . O4 O 0.3772(4) 0.8606(8) -0.1436(5) 0.0177(10) Uani 1 1 d . . . O5 O 0.4447(3) 0.7473(8) 0.3950(5) 0.0132(10) Uani 1 1 d . . . H5 H 0.5061 0.725 0.3466 0.02 Uiso 1 1 d R . . O6 O 0.3982(3) 0.3535(8) 0.1350(5) 0.0120(10) Uani 1 1 d . . . H6 H 0.3708 0.2008 0.1228 0.018 Uiso 1 1 d R . . C1 C 0.3420(5) 0.4121(12) 0.5400(7) 0.0109(13) Uiso 1 1 d . . . C2 C 0.4476(5) 0.5891(13) 0.5302(7) 0.0107(14) Uani 1 1 d . . . H2A H 0.4501 0.7115 0.6185 0.013 Uiso 1 1 calc R . . C3 C 0.3726(5) 0.7461(12) -0.0224(7) 0.0112(14) Uiso 1 1 d . . . C4 C 0.4341(6) 0.4788(12) -0.0031(7) 0.0099(14) Uani 1 1 d . . . H4A H 0.4134 0.3583 -0.088 0.012 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Cu1 0.0123(3) 0.0101(3) 0.0116(4) 0.0021(4) 0.0018(4) 0.0023(3) O1 0.008(2) 0.013(2) 0.014(2) 0.0026(17) -0.0017(19) -0.002(2) O2 0.012(2) 0.014(2) 0.013(2) 0.0036(19) 0.0009(17) -0.0026(18) O3 0.012(2) 0.010(2) 0.012(2) -0.0014(18) 0.0039(18) 0.0035(17) O4 0.023(3) 0.015(2) 0.015(3) 0.0043(19) 0.005(2) 0.005(2) O5 0.012(2) 0.016(2) 0.011(2) 0.0031(19) -0.0011(19) 0.0029(19) O6 0.012(2) 0.006(2) 0.018(3) 0.0013(18) 0.0011(18) -0.0004(18) C2 0.009(3) 0.011(3) 0.012(4) -0.001(3) 0.004(3) -0.001(3) C4 0.013(4) 0.006(3) 0.011(4) 0.001(3) 0.002(3) -0.001(3) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Cu1 O2 1.916(4) 4_556 ? Cu1 O1 1.934(4) . ? Cu1 O3 1.937(4) . ? Cu1 O6 2.050(4) . ? Cu1 O5 2.357(4) . ? O1 C1 1.252(7) . ? O2 C1 1.253(7) . ? O2 Cu1 1.916(4) 4_546 ? O3 C3 1.298(7) . ? O4 C3 1.228(7) . ? O5 C2 1.447(7) . ? O5 H5 0.85 . ? O6 C4 1.449(7) . ? O6 H6 0.8332 . ? C1 C2 1.524(8) . ? C2 C2 1.519(12) 2_665 ? C2 H2A 1 . ? C3 C4 1.525(9) . ? C4 C4 1.563(13) 2_665 ? C4 H4A 1 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 Cu1 O1 93.05(18) 4_556 . ? O2 Cu1 O3 90.83(17) 4_556 . ? O1 Cu1 O3 170.76(18) . . ? O2 Cu1 O6 169.22(18) 4_556 . ? O1 Cu1 O6 95.06(17) . . ? O3 Cu1 O6 82.21(16) . . ? O2 Cu1 O5 99.64(16) 4_556 . ? O1 Cu1 O5 78.03(16) . . ? O3 Cu1 O5 93.06(16) . . ? O6 Cu1 O5 89.00(15) . . ? C1 O1 Cu1 120.2(4) . . ? C1 O2 Cu1 129.8(4) . 4_546 ? C3 O3 Cu1 117.1(4) . . ? C2 O5 Cu1 106.7(3) . . ? C2 O5 H5 109.7 . . ? Cu1 O5 H5 110.1 . . ? C4 O6 Cu1 112.3(3) . . ? C4 O6 H6 113.2 . . ? Cu1 O6 H6 110.7 . . ? O1 C1 O2 126.9(6) . . ? O1 C1 C2 121.4(5) . . ? O2 C1 C2 111.6(5) . . ? O5 C2 C2 109.7(4) . 2_665 ? O5 C2 C1 110.1(5) . . ? C2 C2 C1 108.8(6) 2_665 . ? O5 C2 H2A 109.4 . . ? C2 C2 H2A 109.4 2_665 . ? C1 C2 H2A 109.4 . . ? O4 C3 O3 123.9(6) . . ? O4 C3 C4 119.1(6) . . ? O3 C3 C4 117.0(5) . . ? O6 C4 C3 109.6(5) . . ? O6 C4 C4 110.3(4) . 2_665 ? C3 C4 C4 110.6(6) . 2_665 ? O6 C4 H4A 108.8 . . ? C3 C4 H4A 108.8 . . ? C4 C4 H4A 108.8 2_665 . ? # The following lines are used to test the character set of files sent by # network email or other means. They are not part of the CIF data set # abcdefghijklmnopqrstuvwxyzABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789 # !@#$%^&*()_+{}:"~<>?|\-=[];'`,./ # END of CIF _database_code_depnum_ccdc_archive 'CCDC 927769'